EP2423341B1 - Titanium aluminide alloys - Google Patents
Titanium aluminide alloys Download PDFInfo
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- EP2423341B1 EP2423341B1 EP11187502.7A EP11187502A EP2423341B1 EP 2423341 B1 EP2423341 B1 EP 2423341B1 EP 11187502 A EP11187502 A EP 11187502A EP 2423341 B1 EP2423341 B1 EP 2423341B1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Definitions
- the invention relates to alloys based on titanium aluminides, in particular those produced using melt or powder metallurgical processes, preferably based on y (TiAl).
- Titanium aluminide alloys are characterized by low density, high strength and good corrosion resistance. In the solid state, they have domains with hexagonal ( ⁇ ), biphasic structures ( ⁇ + ⁇ ) and cubic body-centered ⁇ -phase and / or ⁇ -phase.
- alloys are interesting, based on an intermetallic phase ⁇ (TiAI) with tetragonal structure and in addition to the majority phase ⁇ (TiAI) and minority components of the intermetallic phase ⁇ 2 (Ti 3 Al) with hexagonal structure.
- These ⁇ -titanium aluminide alloys are characterized by properties such as low density (3.85 - 4.2 g / cm 3 ), high elastic modulus, high strength and creep resistance up to 700 ° C, making them a lightweight material for high temperature applications make attractive. Examples of this are turbine blades in aircraft engines and in stationary gas turbines, valves in engines and hot gas fans.
- ⁇ -titanium aluminide alloys are highly anisotropic due to their deformation and fracture behavior, but also because of the microstructural anisotropy of the preferred lamellar structure or duplex structure.
- different powder metallurgy and forming methods and combinations of these production methods are used.
- a titanium aluminide alloy which has a structurally and chemically homogeneous structure.
- the majority phases ⁇ (TiAl) and ⁇ 2 (Ti 3 Al) are finely dispersed.
- the disclosed titanium aluminide alloy with an aluminum content of 45 atom% is characterized by exceptionally good mechanical properties and high-temperature properties.
- titanium aluminides have been softened mainly by additions of boron, which lead to the formation of titanium borides (cf. TT Cheng, in: Gamma Titanium Aluminides 1999, Eds. Y.-W. Kim, DM Dimiduk, MH Loretto, TMS, Warrendale PA, 1999, p. 389 , such as Y.-W. Kim, DM Dimiduk, in: Structural Intermetallics 2001, Eds. KJ Hemker, DM Dimiduk, H. Clemens, R. Darolia, H. Inui, JM Larsen, VK Sikka, M. Thomas, JD Whittenberger, TMS, Warrendale PA, 2001, p. 625 .)
- JP-A-06 116691 discloses a method of heat treating titanium aluminide alloys to improve the hardness of the alloys.
- the titanium alloys consist of Ti, 40-50% Al and 3 to 10% of at least one element Nb, Mo and Cr, wherein the alloys may also contain several of the latter elements.
- DE-A-10 2004 056 582 relates to alloys based on titanium aluminides, the alloy compositions consisting of Ti (44.5 to 47) Al (5-10) Nb and Walweise boron and / or carbon.
- the described alloys also contain molybdenum in the range of between 0.1 atom% to 3.0 atom%.
- the alloys are characterized by the fact that they have stable ⁇ phases through the addition of molybdenum over a wide temperature range.
- EP-A-1 889 939 discloses a method for increasing the massive transformation of titanium aluminide alloys with an ⁇ -phase, wherein up to 0.5 at% is introduced into the alloy.
- the alloy may have up to 43 at% of aluminum, 0 to 9 at% of niobium, 0 to 10 at% of tantalum, and 0.01 to 0.15 at% of yttrium
- the present invention seeks to provide a titanium aluminide alloy having a fine grain morphology, especially in the nanometer range. Furthermore, the object is to provide a component with a homogeneous alloy.
- Such composite lamellar structures can be used in alloys via known manufacturing technologies, i. by casting, forming and powder technologies.
- the alloys are characterized by extremely high strength and creep resistance combined with high ductility and fracture toughness.
- Each of said titanium aluminide alloys may optionally comprise the additions of boron and / or carbon, wherein in one embodiment the compositions of said alloys or intermetallic compounds are each optionally (0.1 to 1 at.%) B (boron) and / or ( 0.1 to 1 at.%) C (carbon). As a result, the already fine structure of the alloy is further softened.
- alloys are provided which can be used as a lightweight material for high temperature applications, e.g. Turbine blades or engine and turbine components are suitable.
- the alloys of the invention are prepared using casting metallurgy, melt metallurgy or powder metallurgy techniques, or using these methods in combination with forming techniques.
- the alloys according to the invention are characterized in that they have a very fine microstructure and have high strength and creep resistance combined with good ductility and fracture toughness, in particular with respect to alloys without the composite lamellar structures according to the invention.
- further additives for example of refractory elements
- contain relatively large volume fractions of the ⁇ -phase which may also be present in ordered form as B2 phase.
- the crystallographic lattices of these two phases are mechanically unstable to homogeneous shear processes, which can lead to lattice transformations. This property is mainly due to the anistropic bonding and the symmetry of the cubic body-centered lattice. The inclination of the ⁇ or B2 phase to the lattice transformation is thus pronounced.
- various orthorhombic phases can be formed, including, in particular, phases B19 and B33.
- the invention is based on the idea of utilizing these lattice transformations by shear conversion for additional refining of the microstructure of the titanium aluminide alloys of the present invention. Such a method is not yet known for titanium aluminide alloys in the scientific literature.
- shearing transformations additionally avoid brittle phases such as ⁇ , ⁇ 'and ⁇ ", which are extremely disadvantageous for the mechanical material properties.
- a significant advantage of the alloys according to the invention is that the texture refinement of the alloys without the addition of grain-fining elements or additives such as. Boron (B) is reached and therefore the alloys contain no borides. Since the borides occurring in TiAl alloys are brittle, they lead to the embrittlement of TiAl alloys above a certain content and generally represent potential cracking nuclei in boron-containing alloys.
- the alloys are further characterized in that the corresponding composition has composite lamellar structures with the B19 phase and ⁇ phase in each lamella, the lamellae being surrounded by the TiAl ⁇ phase.
- the ratio, in particular the volume ratio, of the B19 phase and ⁇ -phase in each case is between 0.05 and 20, in particular between 0.1 and 10.
- the ratio, in particular the volume ratio, of the B19 phase and ⁇ phase is in each case in a lamella between 0.2 and 5, in particular between 0.25 and 4.
- a particularly fine microstructure in the alloy composition is characterized in that the ratio, in particular the volume ratio, of the B19 phase and ⁇ Phase in each case between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1.
- lamellae of the composite lamellar structures are surrounded by lamellae of the ⁇ (TiAl) type, preferably on both sides of the lamella.
- the alloys are further characterized in that the lamellae of the composite lamellar structures have a volume fraction of more than 10%, preferably more than 20%, of the entire alloy.
- the fine lamellar structure is retained in the composite structures, if the lamellae of the composite lamellar structures TiAl have the phase ⁇ 2 -Ti 3 Al in a proportion of up to 20%, in particular the (volume) ratio of the B19 phase and ⁇ phase in the lamellae remain unchanged and constant.
- the alloys according to the invention are suitable as high-temperature lightweight materials for components which are exposed to temperatures of up to 800 ° C.
- the object is achieved by a method for producing an alloy described above using from melting or powder metallurgy techniques, wherein after the production of the alloy to an intermediate, further heat treatment of the intermediate at temperatures above 900 ° C, preferably above 1000 ° C, in particular at temperatures between 1000 ° C and 1200 ° C, for a predetermined Duration of more than 60 minutes, preferably more than 90 minutes, is performed, and then the heat-treated alloy is cooled at a predetermined cooling rate of more than 0.5 ° C per minute.
- the heat-treated alloy is cooled at a predetermined cooling rate between 1 ° C per minute to 20 ° C per minute, preferably to 10 ° C per minute.
- the object of the invention is achieved by a component which is produced from an alloy according to the invention, wherein in particular the alloy is produced by melt or powder metallurgical methods or techniques.
- the alloys based on a ⁇ -TiAl intermetallic compound provide lightweight (high temperature) materials or components for use or for use in heat engines such as internal combustion engines, gas turbines, aircraft engines.
- alloys according to the invention with the above-mentioned compositions are preferably prepared by using conventional metallurgical casting methods or by per se known powder metallurgy techniques are produced and can be processed for example by hot forging, hot pressing or hot extrusion and hot rolling.
- the composite lamellar structures are shown below using an alloy with a composition Ti - 42 At% Al - 8.5 At% Nb.
- Fig. 1a shows a photograph of the Gedemandgleiter, which has been recorded by means of a transmission electron microscope.
- the overview in Fig. 1 shows that the composite lamellar structures in Fig. 1 with T, have a streaky contrast to the structures surrounding the structures of the ⁇ -phase.
- Fig. 1b shows a recording of the alloy structure with a higher magnification, wherein it can be seen that the modulated composite lamellar structures (reference symbol T) are surrounded by the ⁇ phase or embedded in the ⁇ phase.
- Fig. 1 c a cast structure of the same alloy Ti-42 atom% Al-8.5 atom% Nb is shown, in which also a composite lamellar structure (reference T) is formed, which is surrounded by the ⁇ -phase.
- Fig. 2a shows in a high-resolution representation the atomic structure of the composite lamellar structures above the ⁇ -phase.
- the composite lamellar structures consist of the ordered B19 phase and the disordered ⁇ phase, which adjoin the ⁇ phase (in the lower region). From the recording in Fig. 2a It can be seen that the composite lamellar structures contain the two crystallographically different phases B19 and ⁇ / B2, which are arranged at intervals of a few nanometers.
- the composite lamellar structures contain phases B19 and ⁇ , both of which are considered ductile.
- the volume ratio of B19 phases and ⁇ phases in a composite lamellar structure is 0.8 to 1.2. Due to the ductile phases B19 and ⁇ , the structure consists essentially of easily deformable lamellae, which are embedded in the relatively brittle ⁇ -phase.
- FIG. 2b The illustration of a B19 structure is shown with an enlarged view.
- the corresponding diffractogram, from the in Fig. 2b shown section and is characteristic of the B19 structure is in Fig. 2c shown.
- Fig. 3 is an electron micrograph of a crack C of the above alloy shown.
- the image shows that the crack C is deflected at the modulated composite lamellar structures (T), and that the composite lamellar structures form ligaments that can bridge the crack edges.
- T modulated composite lamellar structures
- Such a behavior differs significantly from the crack propagation in the previously known Ti-Al alloys, in which a gap fracture occurs in the microscopic scale considered here. In the alloy crack propagation is hindered due to the formed composite lamellar structures.
- the alloys may be formed by the technologies known for TiAl alloys, i. via melt metallurgy, forming technologies and powder metallurgy. For example, alloys are melted in an electric arc furnace and remelted several times and then subjected to a heat treatment.
- the production methods known for primary cast blocks of TiAl alloys may also be used for the production of vacuum arc melting, induction melting or plasma melting.
- hot isostatic pressing may be used as the densification process at temperatures of 900 ° C to 1300 ° C or heat treatments in the temperature range of 700 ° C to 1400 ° C or a combination of these treatments to close pores and to adjust a microstructure in the material.
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Description
Die Erfindung betrifft Legierungen auf der Basis von, insbesondere unter Verwendung von schmelz- oder pulvermetallurgischen Verfahren hergestellten, Titanaluminiden, vorzugsweise auf Basis von y (TiAI).The invention relates to alloys based on titanium aluminides, in particular those produced using melt or powder metallurgical processes, preferably based on y (TiAl).
Titanaluminid-Legierungen zeichnen sich durch eine geringe Dichte, eine hohe Festigkeit und gute Korrosionsbeständigkeit aus. Im festen Zustand weisen sie Domänen mit hexagonaler (α), zweiphasige Strukturen (α + β) sowie kubisch raumzentrierte β-Phase und/oder γ-Phase auf.Titanium aluminide alloys are characterized by low density, high strength and good corrosion resistance. In the solid state, they have domains with hexagonal (α), biphasic structures (α + β) and cubic body-centered β-phase and / or γ-phase.
Für die industrielle Praxis sind insbesondere Legierungen interessant, die auf einer intermetallischen Phase γ (TiAI) mit tetragonaler Struktur beruhen und neben der Majoriätsphase γ (TiAI) auch Minoritätsanteile der intermetallischen Phase α2(Ti3Al) mit hexagonaler Struktur enthalten. Diese γ-Titanaluminid-Legierungen zeichnen sich durch Eigenschaften wie geringe Dichte (3,85 - 4,2 g/cm3), hohe elastische Module, hohe Festigkeit und Kriechfestigkeit bis zu 700°C aus, die sie als Leichtbau-Werkstoff für Hochtemperaturanwendungen attraktiv machen. Beispiele hierfür sind Turbinenschaufeln in Flugzeugtriebwerken und in stationären Gasturbinen, Ventile bei Motoren sowie Heißgasventilatoren.For industrial practice, in particular alloys are interesting, based on an intermetallic phase γ (TiAI) with tetragonal structure and in addition to the majority phase γ (TiAI) and minority components of the intermetallic phase α 2 (Ti 3 Al) with hexagonal structure. These γ-titanium aluminide alloys are characterized by properties such as low density (3.85 - 4.2 g / cm 3 ), high elastic modulus, high strength and creep resistance up to 700 ° C, making them a lightweight material for high temperature applications make attractive. Examples of this are turbine blades in aircraft engines and in stationary gas turbines, valves in engines and hot gas fans.
Im technisch wichtigen Bereich von Legierungen mit Aluminium-Gehalten zwischen 45 Atom % und 49 Atom % treten beim Erstarren aus der Schmelze und beim nachfolgenden Abkühlen eine Reihe von Phasenumwandlungen auf. Die Erstarrung kann entweder vollständig über den β-Mischkristall mit kubisch raumzentrierter Struktur (Hochtemperaturphase) oder in zwei peritektischen Reaktionen erfolgen, an denen der α-Mischkristall mit hexagonaler Struktur und die γ-Phase beteiligt sind.In the technically important range of alloys with aluminum contents between 45 atom% and 49 atom%, a number of phase transformations occur on solidification from the melt and subsequent cooling. The solidification can take place either completely via the β-mixed crystal with cubic body-centered structure (high-temperature phase) or in two peritectic reactions in which the α-mixed crystal with hexagonal structure and the γ-phase are involved.
Ferner ist bekannt, dass Aluminium in γ-Titanaluminid-Legierungen eine Erhöhung der Duktilität und der Oxidationsbeständigkeit bewirkt. Außerdem führt das Element Niob (Nb) zu einer Steigerung der Festigkeit, Kriechfestigkeit, Oxidationsbeständigkeit, aber auch der Duktilität. Mit dem in der γ-Phase praktisch nicht löslichen Element Bor kann eine Kornfeinung sowohl im Gusszustand als auch nach dem Umformen mit anschließender Wärmebehandlung im α― Gebiet erreicht werden. Ein erhöhter Anteil an β-Phase im Gefüge infolge von niedrigen Aluminium-Gehalten und hohen Konzentrationen von β-stabilisierenden Elementen kann zu grober Dispersion dieser Phase führen und eine Verschlechterung der mechanischen Eigenschaften bewirken.It is also known that aluminum in γ-titanium aluminide alloys causes an increase in ductility and oxidation resistance. In addition, the element niobium (Nb) leads to an increase in strength, creep resistance, oxidation resistance, but also the ductility. With the element boron, which is practically insoluble in the γ-phase, grain refining can be achieved both in the cast state and after the forming with subsequent heat treatment in the α-region. An increased proportion of β-phase in the microstructure due to low aluminum contents and high concentrations of β-stabilizing elements can lead to coarse dispersion of this phase and cause a deterioration of the mechanical properties.
Die mechanischen Eigenschaften von γ-Titanaluminid-Legierungen sind aufgrund ihres Verformungs- und Bruchverhaltens, aber auch wegen der Gefügeanisotropie der bevorzugt eingestellten lamellaren Gefüge bzw. Duplex-Gefüge stark anisotrop. Zu einer gezielten Einstellung von Gefüge und Textur bei der Herstellung von Bauteilen aus Titanaluminiden werden Gießverfahren, unterschiedliche pulvermetallurgische und Umform-Verfahren sowie Kombinationen dieser Herstellungsverfahren angewandt.The mechanical properties of γ-titanium aluminide alloys are highly anisotropic due to their deformation and fracture behavior, but also because of the microstructural anisotropy of the preferred lamellar structure or duplex structure. For a specific adjustment of structure and texture in the production of components made of titanium aluminides casting methods, different powder metallurgy and forming methods and combinations of these production methods are used.
Darüber hinaus ist aus
Titanaluminide auf der Basis von γ (TiAI) zeichnen sich im Allgemeinen durch relativ hohe Festigkeiten, hohe elastische Moduln, gute Oxidations- und Kriechbeständigkeit bei gleichzeitig geringer Dichte aus. Aufgrund dieser Eigenschaften sollen TiAI-Legierungen als Hochtemperatur-Werkstoffe eingesetzt werden. Derartige Anwendungen werden durch die sehr geringe plastische Verformbarkeit und die niedrige Bruchzähigkeit stark beeinträchtigt. Hierbei verhalten sich Festigkeit und Verformbarkeit, wie bei vielen anderen Werkstoffen, zueinander invers. Dadurch sind gerade die technisch interessanten hochfesten Legierungen oft besonders spröde. Zur Behebung dieser sehr nachteiligen Eigenschaften wurden umfangreiche Untersuchungen zur Optimierung der Gefüge durchgeführt. Die bisher entwickelten Gefügetypen können grob in a) gleichachsige Gamma-Gefüge, b) Duplexgefüge und c) lamellare Gefüge eingeteilt werden. Der derzeit erreichte Entwicklungsstand ist beispielsweise ausführlich dargestellt in:
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Y.-W. Kim, D.M. Dimiduk, in: Structural Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, CT. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1996, S. 531 -
M. Yamaguchi, H. Inui, K. Ito, Acta mater. 48 (2000), S. 307
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Y.-W. Kim, DM Dimiduk, in: Structural Intermetallics 1997, Eds. MV Nathal, R. Darolia, CT. Liu, PL Martin, DB Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1996, p. 531 -
M. Yamaguchi, H. Inui, K. Ito, Acta mater. 48 (2000), p. 307
Bisher wurden die Gefüge von Titanaluminiden vor allem durch Borzusätze gefeint, die zur Bildung von Titanboriden führen (vgl.
Zur weiteren Feinung und Konsolidierung des Gefüges werden die Legierungen meist mehreren Hochtemperaturumformungen durch Extrudieren bzw. Schmieden unterzogen. Hierzu wird ergänzend auf die folgenden Veröffentlichungen verwiesen:
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Gamma Titanium Aluminides, Eds. Y.-W. Kim, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1995 - ●
Structural Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, CT. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1997 - ●
Gamma Titanium Aluminides 1999, Eds. Y-W. Kim, D.M. Dimiduk, M.H. Loretto, TMS, Warrendale PA, 1999 - ●
Structural Intermetallics 2001, Eds. K.J. Hemker, D.M. Dimiduk, H. Clemens, R. Darolia, H. Inui, J.M. Larsen, V.K. Sikka, M. Thomas, J.D. Whittenberger, TMS, Warrendale PA, 2001
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Gamma Titanium Aluminides, Eds. Y.-W. Kim, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1995 - ●
Structural Intermetallics 1997, Eds. MV Nathal, R. Darolia, CT. Liu, PL Martin, DB Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1997 - ●
Gamma Titanium Aluminides 1999, Eds. YW. Kim, DM Dimiduk, MH Loretto, TMS, Warrendale PA, 1999 - ●
Structural Intermetallics 2001, Eds. KJ Hemker, DM Dimiduk, H. Clemens, R. Darolia, H. Inui, JM Larsen, VK Sikka, M. Thomas, JD Whittenberger, TMS, Warrendale PA, 2001
Eine Arbeitsgruppe um Fritz Appel hat in mehreren Veröffentlichungen Phasenzusammensetzungen in β/B2-Phasen von Titanaluminiden beschrieben, wobei insbesondere die Untersuchungen an der Grundzusammensetzung Ti-(40-44)Al-8,5 Nb (at.%) vorgestellt werden. Hierin ist beschrieben, dass die Legierungen eine neuartige Lamellenstruktur mit den Phasen γ, β/B2 und α2 aufweisen, so unter anderem
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Fritz Appel et al., "Nano-Scale Design of TiAL Alloys Based on Beta-Phase Decomposition", Materials Research Society Symposium Proceedings 980, Seiten 383 bis 388 (2007 - ●
Fritz Appel et al., "Nano Scale Design of TiAL Alloys Based on β-Phase Decomposition", Advanced Engineering Materials 2006, Seiten 371 bis 376 - ●
Fritz Appel et al., "Atomistic Processes of Phase Transformation and Dynamic Recrystallization during Hot-Working of Intermetallic Titanium Alumindes", Material Science Forum 2007, Seiten 465 bis 470
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Fritz Appel et al., "Nano-scale Design of TiAL Alloys Based on Beta Phase Decomposition," Materials Research Society Symposium Proceedings 980, pp. 383-388 (2007 - ●
Fritz Appel et al., "Nano Scale Design of TiAL Alloys Based on β-Phase Decomposition", Advanced Engineering Materials 2006, pages 371-376 - ●
Fritz Appel et al., "Atomic Processes of Phase Transformation and Dynamic Recrystallization during Hot-Working of Intermetallic Titanium Alumindes", Material Science Forum 2007, pages 465-470
In
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Die Veröffentlichung
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Ausgehend von diesem Stand der Technik liegt der vorliegenden Erfindung die Aufgabe zugrunde, eine Titanaluminid-Legierung mit einer feinen Gefügemorphologie, insbesondere im Nanometerbereich, bereitzustellen. Des Weiteren besteht die Aufgabe darin, ein Bauteil mit einer homogenen Legierung bereitzustellen.Based on this prior art, the present invention seeks to provide a titanium aluminide alloy having a fine grain morphology, especially in the nanometer range. Furthermore, the object is to provide a component with a homogeneous alloy.
Gelöst wird diese Aufgabe durch eine Legierung auf der Basis von, insbesondere unter Verwendung von schmelz- oder pulvermetallurgischen Verfahren hergestellten, Titanaluminiden, vorzugsweise auf Basis von γ (TiAl), wobei TiAl-Legierungen mit weiteren Zusätzen Volumenanteile der β-Phase enthalten, die dadurch weitergebildet wird, dass die Zusammensetzung Komposit-Lamellen-Strukturen mit B19-Phase und β-Phase in jeder Lamelle aufweist, wobei das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.05 und 20, insbesondere zwischen 0.1 und 10, beträgt.This object is achieved by an alloy based on, in particular using melt or powder metallurgy produced titanium aluminides, preferably based on γ (TiAl), wherein TiAl alloys containing other additives volume fractions of the β-phase, thereby is further developed that the composition has composite lamellar structures with B19 phase and β-phase in each lamella, wherein the ratio, in particular the volume ratio of the B19 phase and β-phase in each case in a lamella between 0.05 and 20, in particular between 0.1 and 10.
Hierbei weist die Legierung die folgende Zusammensetzung auf:
- Ti - (41 bis 44.5 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) Fe.
- Ti - (41 to 44.5 At%) Al - (5 to 10 At%) Nb - (0.5 to 5 At%) Fe.
Es hat sich gezeigt, dass bei einer derartigen intermetallischen Verbindung Komposit-Lamellen-Strukturen mit Strukturen im Nanometermaßstab erzeugt werden bzw. vorhanden sind, wobei die lamellenartigen Gebilde bzw. modulierte Lamellen aus den kristallographisch unterschiedlichen, alternierend ausgebildeten B19-Phase und β-Phase aufgebaut sind. Hierbei sind die erzeugten Komposit-Lamellen-Strukturen größtenteils von γ-TiAl umgeben.It has been found that in such an intermetallic compound composite lamellar structures are generated with structures on the nanometer scale or are present, wherein the lamellar structures or modulated lamellae of the crystallographically different, alternately formed B19 phase and β-phase constructed are. Here, the composite lamellar structures produced are largely surrounded by γ-TiAl.
Derartige Komposit-Lamellen-Strukturen können in Legierungen über bekannte Herstellungstechnologien, d.h. durch Gießen, Umformen und Pulvertechnologien, hergestellt werden. Die Legierungen zeichnen sich durch extrem hohe Festigkeit und Kriechbeständigkeit bei gleichzeitig hoher Duktilität und Bruchzähigkeit aus.Such composite lamellar structures can be used in alloys via known manufacturing technologies, i. by casting, forming and powder technologies. The alloys are characterized by extremely high strength and creep resistance combined with high ductility and fracture toughness.
Jede der genannten Titanaluminid-Legierungen kann optional die Zusätze von Bor und/oder Kohlenstoff aufweisen, wobei in einer Ausgestaltung die Zusammensetzungen der genannten Legierungen bzw. der intermetallischen Verbindungen jeweils wahlweise (0.1 bis 1 At. %) B (Bor) und/oder (0.1 bis 1 At. %) C (Kohlenstoff) aufweisen. Hierdurch wird das ohnehin schon feine Gefüge der Legierung weiter gefeint.Each of said titanium aluminide alloys may optionally comprise the additions of boron and / or carbon, wherein in one embodiment the compositions of said alloys or intermetallic compounds are each optionally (0.1 to 1 at.%) B (boron) and / or ( 0.1 to 1 at.%) C (carbon). As a result, the already fine structure of the alloy is further softened.
Im Rahmen der Erfindung bestehen bei den angegebenen Legierungszusammensetzungen jeweils die Reste aus Titan und unvermeidbaren Verunreinigungen.In the context of the invention, the residues of titanium and unavoidable impurities exist in the case of the stated alloy compositions.
Damit werden gemäß der Erfindung Legierungen bereitgestellt, die als Leichtbau-Werkstoff für Hochtemperaturanwendungen, wie z.B. Turbinenschaufeln oder Motoren- und Turbinenkomponenten, geeignet sind.Thus, according to the invention, alloys are provided which can be used as a lightweight material for high temperature applications, e.g. Turbine blades or engine and turbine components are suitable.
Die erfindungsgemäßen Legierungen werden unter Verwendung von gießmetallurgischen, schmelzmetallurgischen oder pulvermetallurgischen Verfahren bzw. Techniken oder unter Verwendung dieser Verfahren in Kombination mit Umformtechniken hergestellt.The alloys of the invention are prepared using casting metallurgy, melt metallurgy or powder metallurgy techniques, or using these methods in combination with forming techniques.
Die erfindungsgemäßen Legierungen zeichnen sich dadurch aus, dass sie eine sehr feine Mikrostruktur haben und eine hohe Festigkeit und Kriechbeständigkeit bei gleichzeitig guter Duktilität und Bruchzähigkeit aufweisen, insbesondere gegenüber Legierungen ohne die erfindungsgemäßen Komposit-Lamellen-Strukturen.The alloys according to the invention are characterized in that they have a very fine microstructure and have high strength and creep resistance combined with good ductility and fracture toughness, in particular with respect to alloys without the composite lamellar structures according to the invention.
Es ist bekannt, dass Titanaluminid-Legierungen mit Aluminiumgehalten von 38 - 45 At.% und weiteren Zusätzen beispielsweise von Refraktärelementen relativ große Volumenanteile der β-Phase enthalten, die auch in geordneter Form als B2-Phase vorliegen kann. Die kristallografischen Gitter dieser beiden Phasen sind gegenüber homogenen Scherprozessen mechanisch instabil, was zu Gitterumwandlungen führen kann. Diese Eigenschaft ist im Wesentlichen auf die anistropen Bindungsverhältnisse und die Symmetrie des kubisch raumzentrierten Gitters zurückzuführen. Die Neigung der β- bzw. B2-Phase zur Gittertransformation ist damit stark ausgeprägt. Durch eine Scherumwandlung des kubisch-raumzentrierten Gitters der β- bzw. B2-Phase können verschiedene orthorhombische Phasen gebildet werden, wozu insbesondere die Phasen B19 und B33 gehören.It is known that titanium aluminide alloys with aluminum contents of 38-45 at.% And further additives, for example of refractory elements, contain relatively large volume fractions of the β-phase, which may also be present in ordered form as B2 phase. The crystallographic lattices of these two phases are mechanically unstable to homogeneous shear processes, which can lead to lattice transformations. This property is mainly due to the anistropic bonding and the symmetry of the cubic body-centered lattice. The inclination of the β or B2 phase to the lattice transformation is thus pronounced. By shearing the cubic body centered lattice of the β or B2 phase, various orthorhombic phases can be formed, including, in particular, phases B19 and B33.
Die Erfindung beruht auf dem Gedanken, diese Gittertransformationen durch Scherumwandlung für eine zusätzliche Feinung der Mikrostruktur der erfindungsgemäßen Titanaluminid-Legierungen zu nutzen. Ein derartiges Verfahren ist für Titanaluminid-Legierungen auch in der wissenschaftlichen Literatur bisher nicht bekannt. Bei den oben aufgeführten erfindungsgemäßen Legierungen werden durch die Scherumwandlungen zudem spröde Phasen wie ω, ω' und ω" vermieden, die für die mechanischen Werkstoffeigenschaften äußerst nachteilig sind.The invention is based on the idea of utilizing these lattice transformations by shear conversion for additional refining of the microstructure of the titanium aluminide alloys of the present invention. Such a method is not yet known for titanium aluminide alloys in the scientific literature. In the case of the abovementioned alloys according to the invention, shearing transformations additionally avoid brittle phases such as ω, ω 'and ω ", which are extremely disadvantageous for the mechanical material properties.
Ein wesentlicher Vorteil der erfindungsgemäßen Legierungen besteht darin, dass die Gefügefeinung der Legierungen ohne den Zusatz von Korn-feinenden bzw. Gefüge-feinenden Elementen oder Zusätzen wie z.B. Bor (B) erreicht wird und die Legierungen demnach keine Boride enthalten. Da die in TiAl-Legierungen auftretenden Boride spröde sind, führen sie ab einem bestimmten Gehalt zur Versprödung von TiAl-Legierungen und stellen generell in Borhaltigen Legierungen potenzielle Risskeime dar.A significant advantage of the alloys according to the invention is that the texture refinement of the alloys without the addition of grain-fining elements or additives such as. Boron (B) is reached and therefore the alloys contain no borides. Since the borides occurring in TiAl alloys are brittle, they lead to the embrittlement of TiAl alloys above a certain content and generally represent potential cracking nuclei in boron-containing alloys.
Die Legierungen zeichnen sich weiter dadurch aus, dass die entsprechende Zusammensetzung Komposit-Lamellen-Strukturen mit der B19-Phase und β-Phase in jeder Lamelle aufweist, wobei die Lamellen von der TiAl-γ-Phase umgeben sind.The alloys are further characterized in that the corresponding composition has composite lamellar structures with the B19 phase and β phase in each lamella, the lamellae being surrounded by the TiAl γ phase.
Insbesondere beträgt das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.05 und 20, insbesondere zwischen 0.1 und 10. Weiterhin beträgt das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.2 und 5, insbesondere zwischen 0.25 und 4. Vorzugsweise beträgt das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen (1/3) und 3, insbesondere zwischen 0.5 und 2. Außerdem zeichnet sich eine besonders feine Gefügestruktur in der Legierungszusammensetzung dadurch aus, dass das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.75 und 1.25, insbesondere zwischen 0.8 und 1.2, vorzugsweise zwischen 0.9 und 1.1, beträgt.In particular, the ratio, in particular the volume ratio, of the B19 phase and β-phase in each case is between 0.05 and 20, in particular between 0.1 and 10. Furthermore, the ratio, in particular the volume ratio, of the B19 phase and β phase is in each case in a lamella between 0.2 and 5, in particular between 0.25 and 4. Preferably, the ratio, in particular the volume ratio, of the B19 phase and β-phase in each case in a lamella between (1/3) and 3, in particular between 0.5 and 2. In addition, a particularly fine microstructure in the alloy composition is characterized in that the ratio, in particular the volume ratio, of the B19 phase and β Phase in each case between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1.
Überdies ist es in einer Weiterbildung der erfindungsgemäßen Legierungen möglich, dass Lamellen der Komposit-Lamellen-Strukturen von Lamellen des γ (TiAl)-Typs, vorzugsweise beidseits der Lamelle, umgeben sind.Moreover, it is possible in a development of the alloys according to the invention that lamellae of the composite lamellar structures are surrounded by lamellae of the γ (TiAl) type, preferably on both sides of the lamella.
Die Legierungen zeichnen sich ferner dadurch aus, dass die Lamellen der Komposit-Lamellen-Strukturen ein Volumenanteil von mehr als 10%, vorzugsweise mehr als 20%, der gesamten Legierung haben.The alloys are further characterized in that the lamellae of the composite lamellar structures have a volume fraction of more than 10%, preferably more than 20%, of the entire alloy.
Zudem bleibt die feine lamellenartige Struktur in den Komposit-Strukuren erhalten, wenn die Lamellen der Komposit-Lamellen-Strukturen TiAl die Phase α2-Ti3Al mit einem Anteil von bis zu 20% aufweisen, wobei insbesondere das (Volumen-)Verhältnis von der B19-Phase und β-Phase in den Lamellen unverändert und konstant bleibt.In addition, the fine lamellar structure is retained in the composite structures, if the lamellae of the composite lamellar structures TiAl have the phase α 2 -Ti 3 Al in a proportion of up to 20%, in particular the (volume) ratio of the B19 phase and β phase in the lamellae remain unchanged and constant.
Die erfindungsgemäßen Legierungen eignen sich als Hochtemperatur-Leichtbauwerkstoffe für Bauteile, die Temperaturen von bis zu 800 °C ausgesetzt sind.The alloys according to the invention are suitable as high-temperature lightweight materials for components which are exposed to temperatures of up to 800 ° C.
Darüber hinaus wird die Aufgabe gelöst durch ein Verfahren zum Herstellen einer voranstehend beschriebenen Legierung unter Verwendung von schmelz- oder pulvermetallurgischen Techniken, wobei nach der Herstellung der Legierung zu einem Zwischenprodukt eine weitere Wärmebehandlung des Zwischenprodukts bei Temperaturen oberhalb von 900°C, vorzugsweise über 1000°C, insbesondere bei Temperaturen zwischen 1000°C und 1200°C, für eine vorbestimmte Zeitdauer von mehr als 60 Minuten, vorzugsweise mehr als 90 Minuten, durchgeführt wird, und nachfolgend die wärmebehandelte Legierung mit einer vorbestimmten Kühlrate von mehr als 0.5°C pro Minute abgekühlt wird.In addition, the object is achieved by a method for producing an alloy described above using from melting or powder metallurgy techniques, wherein after the production of the alloy to an intermediate, further heat treatment of the intermediate at temperatures above 900 ° C, preferably above 1000 ° C, in particular at temperatures between 1000 ° C and 1200 ° C, for a predetermined Duration of more than 60 minutes, preferably more than 90 minutes, is performed, and then the heat-treated alloy is cooled at a predetermined cooling rate of more than 0.5 ° C per minute.
Insbesondere wird die wärmebehandelte Legierung mit einer vorbestimmten Kühlrate zwischen 1 °C pro Minute bis 20°C pro Minute, vorzugsweise bis 10°C pro Minute, abgekühlt.More specifically, the heat-treated alloy is cooled at a predetermined cooling rate between 1 ° C per minute to 20 ° C per minute, preferably to 10 ° C per minute.
Weiterhin wird die Aufgabe der Erfindung durch ein Bauteil gelöst, das aus einer erfindungsgemäßen Legierung hergestellt ist, wobei insbesondere die Legierung durch schmelz- oder pulvermetallurgische Verfahren oder Techniken hergestellt ist. Durch die Legierungen auf der Basis einer intermetallischen Verbindung vom Typ γ-TiAl werden leichte (Hochtemperatur-)Werkstoffe oder Bauteile für den Einsatz oder zur Verwendung in Wärmekraftmaschinen, wie Verbrennungsmotoren, Gasturbinen, Flugtriebwerken bereitgestellt.Furthermore, the object of the invention is achieved by a component which is produced from an alloy according to the invention, wherein in particular the alloy is produced by melt or powder metallurgical methods or techniques. The alloys based on a γ-TiAl intermetallic compound provide lightweight (high temperature) materials or components for use or for use in heat engines such as internal combustion engines, gas turbines, aircraft engines.
Überdies besteht eine weitere Lösung der Aufgabe in einer Verwendung einer erfindungsgemäßen, voranstehend beschriebenen Legierung zur Herstellung eines Bauteils. Zur Vermeidung von Wiederholungen wird auf die obigen Ausführungen ausdrücklich verwiesen.Moreover, a further solution of the problem is a use of an alloy according to the invention, described above, for the production of a component. To avoid repetition, reference is expressly made to the above statements.
Die erfindungsgemäßen Legierungen mit den oben aufgeführten Zusammensetzungen werden vorzugsweise durch Verwendung herkömmlicher metallurgischer Gießmethoden oder durch an sich bekannte pulvermetallurgische Techniken erzeugt und können beispielsweise durch Warmschmieden, Warmpressen bzw. Warmstrangpressen und Warmwalzen bearbeitet werden.The alloys according to the invention with the above-mentioned compositions are preferably prepared by using conventional metallurgical casting methods or by per se known powder metallurgy techniques are produced and can be processed for example by hot forging, hot pressing or hot extrusion and hot rolling.
Nachfolgend werden anhand einer Legierung mit einer Zusammensetzung Ti - 42 Atom % Al - 8.5 Atom % Nb die Komposit-Lamellen-Strukturen gezeigt.The composite lamellar structures are shown below using an alloy with a composition Ti - 42 At% Al - 8.5 At% Nb.
Die in
In
In
In
Die für technische Anwendungen wichtige Bruchzähigkeit von Gefügen wurde mit Hilfe von gekerbten Chevron-Proben im Biegetest bei unterschiedlichen Temperaturen bestimmt. Die aufgenommene Registerkurve eines solchen Tests ist in
Die Legierungen können durch die für TiAl-Legierungen bekannten Technologien, d.h. über Schmelzmetallurgie, Umformtechnologien und Pulvermetallurgie hergestellt werden. Beispielsweise werden Legierungen in einem Lichtbogenofen geschmolzen und mehrfach umgeschmolzen und anschließend einer Wärmebehandlung unterzogen. Darüber hinaus können zur Herstellung auch die für Primärgussblöcke aus TiAl-Legierungen bekannten Herstellverfahren Vakuum-Lichtenbogen-Schmelzen, Induktionsschmelzen oder Plasma-Schmelzen verwendet werden. Gegebenenfalls können nach dem Erstarren von Guss-Primärgussmaterial heiß-istostatisches Pressen als Verdichtungsverfahren bei Temperaturen von 900°C bis 1.300°C oder Wärmebehandlungen im Temperaturbereich von 700°C bis 1.400°C oder eine Kombination dieser Behandlungen angewendet werden, um Poren zu schließen und eine Mikrostruktur im Material einzustellen.The alloys may be formed by the technologies known for TiAl alloys, i. via melt metallurgy, forming technologies and powder metallurgy. For example, alloys are melted in an electric arc furnace and remelted several times and then subjected to a heat treatment. In addition, the production methods known for primary cast blocks of TiAl alloys may also be used for the production of vacuum arc melting, induction melting or plasma melting. Optionally, after the solidification of cast primary material, hot isostatic pressing may be used as the densification process at temperatures of 900 ° C to 1300 ° C or heat treatments in the temperature range of 700 ° C to 1400 ° C or a combination of these treatments to close pores and to adjust a microstructure in the material.
Claims (12)
- An alloy based on titanium aluminides, particularly made with the use of fusion or powder metallurgical processes, preferably on the basis of γ (TiAl), wherein TiAl alloys with further additives contain volumetric fractions of the β phase, characterised in that the composition includes composite lamellar structures with B19 phase and β phase in each lamella, wherein the ratio, particularly the volumetric ratio, of the B19 phase and the β phase in each lamella is between 0.05 and 20, particularly between 0.1 and 10, wherein the alloy has the following composition:Ti - (41 to 44.5 at %) Al - (5 to 10 at %) Nb - (0.5 to 5 at %) Fe.
- An alloy as claimed in claim 1, characterised in that the ratio, particularly the volumetric ratio, of the B19 phase and the β phase in each lamella is between 0.2 and 5, particularly between 0.25 and 4.
- An alloy as claimed in claim 1 or 2, characterised in that the ratio, particularly the volumetric ratio, of the B19 phase and β phase in each lamella is between (1/3) and 3, particularly between 0.5 and 2.
- An alloy as claimed in one of claims 1 to 3, characterised in that the ratio, particularly the volumetric ratio, of the B19 phase and β phase in each lamella is between 0.75 and 1.25, particularly between 0.8 and 1.2, preferably between 0.9 and 1.1.
- An alloy as claimed in one of claims 1 to 4, characterised in that the composition selectively includes (0.1 to 1 to 1 at %) B (boron) and/or (0.1 to 1 at %) C (carbon).
- An alloy as claimed in one of claims 1 to 5, characterised in that lamellas of the composite lamellar structures are surrounded by lamellas of the γ (TiAl) type, preferably on both sides of the lamella.
- An alloy as claimed in one of claims 1 to 6, characterised in that the lamellas of the composite lamellar structures have a volumetric proportion of more than 10%, preferably more than 20%, of the alloy.
- An alloy as claimed in one of claims 1 to 7, characterised in that the lamellas of the composite lamellar structures include the phase α2-Ti3Al in a proportion of up to 20%.
- A method of making an alloy as claimed in one claims 1 to 8 using fusion or powder metallurgical techniques, wherein after making the alloy into an intermediate product a further heat treatment of the intermediate product is performed at temperatures above 900°c, preferably above 1000°c, particularly at temperatures between 1000°c and 1200°c for a predetermined period of time of more than 60 minutes, preferably more than 90 minutes and subsequently the heat-treated alloy is cooled at a predetermined cooling rate of more than 0.5°C per minute.
- A method as claimed in claim 9, characterised in that heat-treated alloy is cooled at a predetermined cooling rate of between 1°c per minute to 20°c per minute, preferably to 10°c per minute.
- A component which is made of an alloy as claimed in one of claims 1 to 8, wherein, in particular, the alloy is made by fusion or powder metallurgical methods or techniques.
- Use of an alloy as claimed in one of claims 1 to 8 for making a component.
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DE102007060587A DE102007060587B4 (en) | 2007-12-13 | 2007-12-13 | titanium aluminide |
EP08020431.6A EP2075349B1 (en) | 2007-12-13 | 2008-11-25 | Titanium aluminide alloys |
EP09010152.8A EP2145967B1 (en) | 2007-12-13 | 2008-11-25 | Titanium aluminide alloys |
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CN110438369A (en) * | 2019-09-18 | 2019-11-12 | 大连大学 | A kind of high rigidity, the preparation method of high oxidative Ti-Al-Nb-Re alloy |
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DE10351946A1 (en) * | 2003-03-21 | 2004-10-07 | Dechema Gesellschaft Für Chemische Technik Und Biotechnologie E.V. | Process for treating the surface of a component consisting of an AL alloy, in particular a TiAL alloy, and the use of organic halocarbon compounds or halides incorporated in an organic matrix |
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US10544485B2 (en) | 2016-05-23 | 2020-01-28 | MTU Aero Engines AG | Additive manufacturing of high-temperature components from TiAl |
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EP2145967A3 (en) | 2010-04-21 |
EP2075349B1 (en) | 2016-03-09 |
JP5512964B2 (en) | 2014-06-04 |
RU2466201C2 (en) | 2012-11-10 |
EP2075349A2 (en) | 2009-07-01 |
DE102007060587A1 (en) | 2009-06-18 |
CN101457314A (en) | 2009-06-17 |
US20090151822A1 (en) | 2009-06-18 |
EP2075349A3 (en) | 2009-09-09 |
CN101457314B (en) | 2013-07-24 |
BRPI0806979A2 (en) | 2010-04-20 |
RU2008149177A (en) | 2010-06-20 |
EP2145967A2 (en) | 2010-01-20 |
EP2145967B1 (en) | 2013-07-24 |
US20140010701A1 (en) | 2014-01-09 |
DE102007060587B4 (en) | 2013-01-31 |
JP2009144247A (en) | 2009-07-02 |
CA2645843A1 (en) | 2009-06-13 |
IL195756A0 (en) | 2009-11-18 |
US20100000635A1 (en) | 2010-01-07 |
KR20090063173A (en) | 2009-06-17 |
EP2423341A1 (en) | 2012-02-29 |
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